Partial dehydrohalogenation of haloalkylhalobicycloalkenic compounds



United States Patent Q r 3,090,817 PARTIAL DEHYDROHALOGENATIGN F HAM)-ALKYLHALGBKCYCLOALKENIC COMP'SUNDS Louis Schmerling, Riverside, 111.,assignor to Universal Oil Products Company, Des Plaines, 111., acorporation of Delaware No Drawing. Filed July 27, 1960, Ser. No. 45,55118 Claims. (Cl. 260-648) This application is a continuation-in-part ofmy copending application Serial No. 803,587, filed April 2, 1959, nowabandoned, which was a continuation-in-part of my co-pending applicationSerial No. 580,468, filed April 25, 1956, now abandoned.

The present invention relates to methods for partiallydehydrohalogenating certain haloalkylhalobicycloolefinic compounds andmore particularly to a method of dehydrohalogenatinghaloalkylhalobicycloheptenes.

Heretofore it has been indicated that bicycloalkadienes could not beprepared by dehalogenating halobicycloalkenes obtained by thecondensation of a cycloalkadiene with a haloolefin. For example,attempts have been made, as disclosed in a paper by Roberts et al.,Journal of the American Chemical Society, 72, 3329 (1950), and inBelgian Patent No. 498,176, issued to I. Hyman et al., todehydrochlorinate chlorobicyclo[2.2.1]-2-heptene to formbicyclo[2.2.l]-2,5-heptadiene, also known as 2,5-norbornadiene. This isillustrated by the following equation:

01 KOH +HC=CHC1 C No reaction On the other hand, partial dehalogenationof the condensation product of a halogenated cycloalkadiene, namely,hexachlorocyclopentadi ne and vinyl chloride may be carried out as shownby the following equations:

However, this dehydrochlorination reaction occurs because of thepresence of the six chlorine atoms on one ring of the molecule, saidchlorine atoms serving to activate the chlorine atom on the second ring.As hereinbefore stated it has been shown that the reaction product of aconjugated cycloalkadiene such as an unhalogenated cyclopentadiene and amonohaloolefin will not undergo dehydrohalogenation when subjected tothe operating conditions of prior processes, the single halogen atombeing too inert to undergo reaction with the dehydrohalogenating agent.

However, I have now discovered that the products of the Diels-Aldercondensation of cycloalkadienes with a particular class ofpolyhaloolefins contain active halogens and, contrary to the teaching ofthe prior art, may be partially dehydrohalogenated to introduce anolefinic bond into a compound having the bicycloheptane ring systemwhich previously was regarded as not susceptible to dehydrohalogenation,thus forming the desired halosubstituted bicycloalkenes. The compoundswhich I subject to dehydrohalogenation are characterized by the presenceof halogen on only one of the rings and on a side-chain alkyl group.Furthermore, not more than two halogen atoms are attached to the ring.That these compounds undergo dehydrohalogenation is unexpected; the veryfact that the literature of the prior art now known shows that acyclopentadiene-vinyl chloride adduct cannot be dehydrochlorinated whilethe hexachlorocyclopentadiene-vinyl chloride adduct can bedehydrochlorinated would tend to lead away from the process of thepresent invention inasmuch as it would appear that a chlorine atom of abicyclic chlorinated compound cannot be removed by treatment with adehydrochlorinating agent unless one of the rings is completelychlorinated.

It is therefore an object of this invention to prepare ahalo-substituted alkylbicyclo alkadiene by partially dehydrohalogenatinga haloalkylhalobicycloalkene.

The term bicycloalkadiene as used hereinafter in the specification andappended claims, refers to those compounds in which both double bondsare in the ring and to those compounds in which one of the double bondsis in the ring, the other double bond being exo thereto. The expressionhalo-substituted bicycloalkadiene refers to bicycloalkadienes whichcontain halogen attached to a carbon atom in the ring and/ or aside-chain. Thus, both 2-chloromethyl-2,S-norbornadiene and 5-chloromethylene-Z-norbornene are halo-substituted bicycloalkadienes.

A further object of this invention is to first prepare ahaloalkylhalobicycloalkene and then to partially dehydrohalogenate thesame to form a halo-substituted bicycloalkadiene.

One embodiment of this invention is found in a process for thepreparation of a halo-substituted bicycloalkadiene which comprisescondensing a conjugated cycloalkadiene with a haloolefin having thegeneral formula:

in which R is a haloalkyl radical, Q and Q are radicals selected fromthe group consisting of hydrogen and halogen radicals, only one of saidQ and Q radicals being halogen, and R is a radical selected from thegroup consisting of hydrogen, alkyl, halogen, haloalkyl, cycloalkyl andaryl radicals, thereby forming a haloalkylhalobicycloalkene, andpartially dehydrohalogeiiating said alkene in the presence of adehydrohalogenating agent selected from the group consisting of alkalimetal hydroxides, alkaline earth metal hydroxides, alkali metalalkoxides and amines at a temperature in the range of from about 50 toabout 250 C. to form a halo-substituted bicycloalkadiene.

A further embodiment of the invention is found in a process for thepreparation of a halo-substituted bicycloheptadiene which comprisescondensing cyclopentadiene with a haloolefin having the general formula:

in which R is a haloalkyl radical, Q and Q' are radicals selected fromthe group consisting of hydrogen and halogen radicals, only one of saidQ and Q radicals being halogen, and R is a radical selected from thegroup consisting of hydrogen, alkyl, halogen, haloalkyl, cycloalkyl andaryl radicals, thereby forming a haloalkylhalobicycloheptene, andpartially dehydrohalogenating said heptene in the presence of adehydrohalogenating agent comprising an alkali metal hydroxide and anorganic solvent at a temperature in the range of from about 50 3 toabout 250 C. to form a halo-substituted bicycloheptadiene.

Yet another embodiment of the invention resides in a halogenated-alkylidene-2-norbornene.

A specific embodiment of the invention resides in a process for thepreparation of a halo-substituted bicycloheptadiene which comprisescondensing cyclopentadiene with 2,3-dichloro-1-propene, thereby formingS-chloro-S- chloromethyl-2-norbornene, and partially dehydrohalogenatingsaid heptene in the presence of potassium hydroxide and ethanol at atemperature in the range of from about 7 5 to about 200 C. to formS-chloromethylene- Z-norbornene and 2-chloromethyl-2,S-norbornadiene.

. Yet another specific embodiment of the invention is found in5-chloromethylene-2-norbornene.

Other objects and embodiments referring to alternative reactantsutilizable as charging stock in the present process and to alternativedehydrohalogenating agents within the scope of this invention will bereferred to in greater detail in the following further detaileddescription of the invention.

As hereinbefore set forth it has now been discovered thathalo-substituted bicycloalkadienes having the following formula:

. 7 RI! RII in which R represents a haloalkyl radical, X represents ahydrogen, halogen, alkyl or haloalkyl radical, y is an integer from 1 to4, preferably 1 or 2, R" is independently selected from the groupconsisting of hydrogen and alkyl radicals and R is a hydrogen, halogen,alkyl or haloalkyl radicals, may be synthesized by condensing, in aDiels-Alder condensation reaction, a conjugated cycloalkadiene with apolyhaloolefin having the general formula:

i Q Q in which R is a haloalkyl radical, R is a radical selected fromthe group consisting of hydrogen, alkyl, halogen, haloalkyl, cycloalkyland aryl radicals, Q and Q are hydrogen or halogen radicals, only one ofsaid Q and Q radicals being halogen, to form ahaloalkylhalobicycloalkene, and dehydrohalogenating the resultantcompound in the presence of a dehydrohalogenating agent, thus yieldingnew compositions of matter comprising the desired halosubstitutedbicycloalkadienes.

. The reaction between the conjugated cycloalkadiene and thepolyhaloolefin is a thermal condensation of the Diels- Alder type andoccurs in the absence of any added catalyst. The condensation usuallytakes place at a temperature in the range of from about 50 to about 250C., and preferably in the range of from about 100 to about 200 C. Inaddition, the reactants are preferably present in a molar ratio range offrom about 0.5 :1 to about 0.9:1 moles of cycloalkadiene topolyhaloolefin. The excess of polyhaloolefin is preferred in order toinsure the production of a bicyclic compound instead of a tetracyclic'compound which may occur if the cycloalkadiene is in excess.

7 The halo-substituted bicycloalkadienes comprising new compositions ofmatter which are the desired products of the present invention areusefulas intermediates in the preparation of insecticides,pharmaceuticals, resins and plastics. For example, the condensation of ahaloalkylbicycloalkadiene such as 2-chloromethyl-2,S-norbornadieneprepared according to the process of this invention, withhexachlorocyclopentadiene yieldsl,2,3,4,10,10-hexachloro-6-chloromethyl-1,4,4a,5,8,8a-hexahydro 1,4,5,8-

dimethanonaphthalene;

This reaction is illustrated by the following equation:

01 o1 01 c1 IW GHCl 01 I ono1 +I o I c1001 o 01 01 or I I The reactionbetween the conjugated cycloalkadiene such as cyclopentadiene and apolyhaloolefin such as a 2,3- dihalo-l-propene will proceed according tothe following equation:

The polyhaloalkylbicycloalkene will then be partially dehydrohalogenatedin the presence of a dehydrohalogenating agent such as an alkali metalhydroxide and an organic solvent according to the following equation: I

\"CHsX MOH CHaX I OHX X LG I and I C I I I/ i I ROH to prepare thedesired halo-substituted bicycloalkadiene. In the above equations Xrepresents a halogen, MOI-I is an alkali metal hydroxide and ROI-I is analcohol.

Another, more specific, example of the above method of preparing ahalo-substituted bicycloalkadiene is found in the'following equations inwhich cyclopentadiene is reacted with 1,3-dichloro-l-propene and theresulting compound comprising 6-chloro-5-chloromethyl-Z-norbornene isdehydrohalogenated in the presence of potassium hydroxide and ethanol toform the desired 2-chloromethyl- 2,5-norbornadiene and6-chloro-5-met'hylene-2-norbornene.

. I ITOH CI KOH I 011201 I on,

C I C I and I O I/ ethanol I I/ As hereinbefore stated one component ofthe feed stock is selected from the group of compounds consisting ofconjugated cycloalkadienes, such compounds including 1,3-cyclopentadiene (herein referred to as cyclopentadiene),

1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3cyclooctadiene, etc., alkylsubstituted cyclopentadienes such as 1- methylcyclopentadiene,2-methylcyclopentadiene, 5-meth-' ylcyclopentadiene,S-ethylcyclopntadiene, 5,5-dimethyl- HgOl cyclopentadiene,1,2-dimethylcyclopentadiene, etc., 1- rnethyl-1,3-cyclohexadiene, 1ethyl-1,3-cyclohexadiene, 1,2-dimethyl-1,3-cyclohexadiene,1,3-dimethyl-1,3cyclohexadiene, 1,Z-diethyl-1,3-cyclohexadiene, etc.Cyclopentadiene and alkyl substituted cyclopentadienes are preferredreactants in this process due to their relatively greater availability.It is also contemplated within the scope of this invention thatdicycloalkadienes which disassociate and become monocycloalkadienes atconditions under which the reaction of this invention proceeds may alsobe used. Examples of these dicycloalkadienes include dicyclopentadiene,dicyclohexadiene, etc.

The polyhaloolefin compound which as hereinbefore set forth has thegeneral formula:

in which R, R, Q and Q represent radicals previously set forth, mayinclude 1,3-dichloro-1-propene,

1, 3-dibromo-l-propene, 1,3-dilluoro-l-propene, 1,3-diiodo-l-propene,2,3-dichloro-1-propene, 2,3-dibromo-1-propene, 2,3-diiiuoro-1-propene,2,3-diiodol-propene, 1,3,3-trichloro-1-propene,1,3,3-tribromo-l-propene, ,1,3-trichloro-l-propene,1,3-tribromo-l-propene, 1,3-trifluoro-1-propene,

,1,3-triiodo-1-propene,

,3 ,3-trichloro'l -propene, ,3,3-tribron1o-1-propene,,3,3-tritluoro-1-propene, ,3,3-triiodo-1-propene,

,3 ,3,3-tetrachlorol -propene, ,3,3 ,S-tetrabromol-propene, ,3,3,3-tetrafiuorol-propene, ,3,3,3-tet-raiodo-1-propene, ,3,3,3-tetrachlorol-propene, ,3 3 ,3-tetrabromo-l-propene,,3,3,3-tetrafiuorol-propene, 2,3 ,3,3-tetraiodo-l -propene,1,4-dichloro-1-butene,

1 ,4 dibromo-l-butene, 1,4-difiuoro-1-butene, 1,4-diiodo-l -butene, 2,rdichloro-1-butene, 2,4-dibromo-1-butene, 2,4-difluoro-1-butene,2,4-diiodol-butene, 1,4,4-trichloro- Lbutene,

l ,4,4-tribromo-lbutene, 1,4,4-trifluoro-1-butene,1,4,4triiodo-1-butene, 1,4,4,4'tetrachloro-l -butene,1,4,4,4-tetrabromol-butene, 1,4,4,4-tetrafiuorol-butene,1,4,4,4-tetraiodol-butene, 2,4,4-trichlorol -butene,2,4,4-tribromo-1-butene, 2,4,4-trifiuoro-1-butene,2,4,4-triiodo-1-butene, 2,4,4,4-tetrachl0ro-1 butene,2,4,4,4-tetrabromo-l-butene, 2,4,4,4-tetrafiuoro-l-butene,2,4,4,4-tetraiodol-butene, l,3-dichloro-2-butene,

1 ,3-dibromo-2-butene, 1,3-difiuoro-2-butene, 1,3-diiodo-2-butene,1,2-dichloro-2-butene,

,Z-dibrorno-Z-butene, ,Z-difluoIO-Z-butene, ,2-diiodo-2-butene,

,1, 3-trichloro-2-butene, ,1,3-tribromo-2-butene,

, l ,3-trifiuoro-2-butene, ,1,3-triiodo-2-butene,

, 1,2-trichloro-2-butene,

, 1,2-tribro1no-2-butene, ,1,2-trifluoro-2-butene,

, 1 ,Z-triiodo-Z-butene, ,1,1,S-tetrachloro-Z-butene,,l,1,3-tetrabromo-2-butene,

, 1,1 ,3-tetrafluoro-2-butene, ,l,1,3-tetraiodo-2-butene,

, 1, l,2-tetrachloro-2 butene,

, 1, l ,2-tetrabromo-2-butene,

l 1,2-tetrafluoro-2-butene, 1,l,1,2-tetraiodo-2-butene, l-cyclopentyl-Z,3-dichlorol-propene, l-cyclopentyl-2,3-dibromol-propene1-cyclopentyl-2,3-difluoro-l-propene, 1-cyclopentyl-2,3-diiodo-1-propene, 1-cycloheXyl-2,3-dichlorol-propene, 1 -cycloheXyl-2, 3-dibromo-1-propene, 1-cycloheXyl-2,3difiuoro-1-propene,1-cycloheXyl-2,3-diiodo-1 -propene, 1-phenyl-2, 3 -dichlor0-1-propene,1-phenyl-2,3-dibrornol-propene, l-phenyl-2,3-difiuoro- 1 -propene,1-phenyl-2,3-diiodo-l-propene, 1-cyclopentyl-2,4-dichloro-1=butene,1cyclopentyl-2,4-dibrom0- 1 -butene, 1-cyclopentl-2,4-difiuoro-l-butene, 1-cyclopentyl-2,4-diiodo-1-butene,1-cyclohexyl-2,4-dichloro-1 butene, 1-cyclohexyl-2,4-dibromol-butene,l-cyclohexyl-2,4-difiuorol-butene, 1-cycloheXyl-2,4-diiodol-butene,1-phenyl-2,4-dichlorol-butene, 1-phenyl-2,4-dibromo-1-butene,1-phenyl-2,4-difiuo rol-butene, 1-phenyl-2,4-diiodo-1-butene, etc.

1 1 l 1 l 1 1 1 l 1 l 1 l l 1 1 1 l The dichloropropenes are thepreferred polyhaloolefins due to their relatively greater availabilityand lower cost, and also due to the fact that they will result in theformation of the preferred final products. It is to be understood thatthe above enumerated conjugated cycloalkadienes and polyhaloolefins ofthe aforesaid general formula are only representatives of the compoundswhich may be used, and that this invention is not necessarily limitedthereto.

The partial dehydrohalogenation of the polyhaloalkylbicycloalkenesresulting from the reaction between the conjugated cycloalkadiene andthe polyhaloolefin is effected by treating said compounds with adehydrohalogenating agent which includes the hydroxides of the alkalimetals and alkaline earth metals such as the hydroxides of lithium,sodium, potassium, rubidium, cesium, calcium, barium, and strontium;amines such as trimethylamine, pyridine, quinoline, etc.; alkali metalalkoxides such as sodium methoxide, potassium ethoxide, etc.; and otherbasic substances such as potassium carbonate, potassium phenoxide, etc.The hydroxides of the alkali metals and alkaline earth metals may beused as such (fused or powdered) or they may be dissolved in a suitableorganic solvent, preferably an alcohol. The particular alcohol which isused as the organic solvent in the dehydrohalogenating reaction willdepend largely upon the temperature at which the reaction occurs.Alcohols which are utilizable in this reaction include methyl, ethyl,npropyl, isopropyl, n-butyl, isobutyl, amyl, etc.

The operating conditions under which the process of the presentinvention is conducted will, to some extent, depend upon the particularcompounds employed in the reaction. The temperature for the reactionbetween the particular conjugated cycloalkadiene and the polyhaloolefinin which a haloalkylhalobicycloalkene is formed will range from aboutatmospheric to about 250 C. or more, the preferred range being fromabout 100 to about 200 C. Likewise, the partial dehydrohalogenation stepof this process will also occur at temperatures depending upon theparticular reactants and the solvent which is used as a medium for thereaction. Suitable temperatures will usually lie in the range of fromabout 50 to about 250 C., the preferred range being from 75 to about 200C. In addition, the reaction will usually take place at atmosphericpressure, however, when the reaction temperature is in a higher rangethan the boiling point of the solvent, superatmospheric pressures may beemployed.

The process of this invention may be effected in any suitable manner andmay comprise eitherv a batch or a continuous type operation. When abatch type operation is used, a quantity of the reactants comprising theconjugated cycloalkadiene and the polyhaloolefin is placed in a reactorprovided with a mixing and heating device. The reactor is heated to thedesired temperature while thoroughly admixing the contents thereof.After a suitable period of time has elapsed, the reactor and itscontents are cooled to room temperature, after which the desired productis recovered by suitable means, for example, by fractional distillationor other means known in the art, while the unreacted feed stock may bere charged to form a portion of the starting material of the next batch.The desired product is then placed in a second reactor, or if sodesired, returned to the same reactor and the dehydrohalogenating agentand organic solvent added thereto. The reactor is then heated to thedesired temperature until the reaction is completed, after which thehalo-substituted bicycloalkadiene is separated by suitable meanshereinbefore set forth while the organic solvent and dehydrohalogenatingagent are recovered for further use in subsequent batches.

Another method of operation of the present process is of the continuoustype. In this operation the reactants comprising the conjugatedcycloalkadiene and the polyhaloolefin are continuously charged to areactor provided with heating and mixing means. The reactor may comprisean unpacked vessel or coil or may be lined with an adsorbent packingmaterial such as dehydrated bauxite, alumina and the like, said reactorbeing maintained at suitable operating conditions of temperature andpressure. The desired reaction product comprising ahaloalkylhalobicycloalkene is continuously withdrawn from this vessel bysuitable means and charged into a second reactor also maintained atsuitable operating conditions, while the unreacted feed stock from thefirst reactor may be withdrawn and recycled for use as a part of thefresh feed stock. The dehydrohalogenating agent, comprising, forexample, an alkali or alkaline earth hydroxide, either in solid orfluidized form or dissolved in the solvent which acts as a medium inwhich the partial dehydrohalogenation takes place are also charged tothe aforesaid second reactor by suitable means. The partiallydehydrohalogenated compound, comprising a halo-substitutedbicycloalkadiene, is continuously withdrawn from this second reactor andpurified by conventional means hereinbefore set forth, while theunreacted material may be recycled to form a portion of the feed stock.

As hereinbefore set forth, the halo-substituted bicycloalkadieneprepared in the above manner may be reacted with apolyhalocycloalkadiene such as hexachyorocyclopentadiene to formpolyhaloalkyl tetracyclic compounds which are useful as insecticides.The condensation of the halo-substituted bicycloalkadiene and thehexachlorocyclopentadiene is carried out in a similar manner to thereaction between the conjugated cycloalkadiene and the polyhaloolefin ashereinbefore described. The temperature at which the reaction is to becarried out will be in the range of from about atmospheric to about 250C.

. actor provided with heating and mixing devices.

or more, the preferred range being from about 60 to about 200 C. Inaddition, the reaction may be effected in any suitable manner, either abatch or a continuous type operation similar to that hereinbeforedescribed with reference to the reaction between the cycloalkadiene andthe polyhaloolefin. in the batch type operation the reactants comprising.the hexachlorocyclopentadiene and the halosubstituted bicycloalkadieneare placed in a re- This reactor is heated and maintained at the desiredtemperature until the reaction is completed after which the reactor iscooled to room temperature and the desired reaction product withdrawn,separated and purified by conventional means such as fractionaldistillation, crystallization, etc.

When a continuous type operation is used the reactants may be introducedinto a reactor through lines provided therefor, said reactor beingequipped with heating and mixing means and maintained at the desiredoperating conditions of temperature and pressure. The desired product iswithdrawn and purified while the unconverted material may be recycledand used as part of the feed stock, or mixed with fresh startingmaterials. It is also contemplated within the scope of this invention,that this latter reaction may take place in the presence of inertdiluents, e.g. liquid aromatic hydrocarbons such as benzene, toluene,etc.

The physical properties of the insecticides which are prepared byreacting the products of this invention with other organic compoundssuch as hexachlorocyclopenta diene, the illustrative reactions of saidreactions being hereinbefore set forth, and the effects they have onentomological forms of life make them particularly desirable asinsecticides and insect repellents, the compounds having many ofthe'features desired of materials for this purpose. are destructive ofplant life and materials normally subject to insect infestation, theirtoxic effects being mani tested by contact of the poison with theinsect. The involatility to'be retained on the insect for the timerequired to accomplish the toxic effect of the compounds. The volatilityand retentive capacity of the compounds may be varied at will bycombining them with suitable fixing agents which reduce or promote theirvolatilization,

1 as desired. Thus, the compounds may be dissolved in a suitable highboiling solvent, such as a mineral or vegetable oil, petroleum, etc.; awax, such as paraflin wax, beeswax, etc.; a high molecular weightalcohol or ether such as myricyl alcohol, dibutyl ether, etc.; or theymay be emulsified with water by the addition of an emulsifying agent,such as a surface active agent, to the mixture of components. The lattersolvents and dispersants may also be employed for the specific purposeof reducing the concentration of insecticide to the desired level in aspecific insecticidal formulation. The particular formulation of activecomponents in combination with the solvent or dispersant will dependupon its application. Compositions containing as high as 20% of activecom ponent may be preferred, in some instances where deep penetration ofthe insecticide is desired, as in the treat ment of fibrous material,such as wood, for extinction of a particular infestation, for example,wood termites. For other purposes the required concentration of activecomponents in the formulation may be as low as 0.1%,

moth larvae.

They are, for example, toxic to insects which In utilizing the presentinsecticidal compounds against most insects, a composition containingfrom about 0.1% to about by weight of the active component is highlyeffective. The choice of the most desirable solvent or dispersantfurther depends upon the method utilized to apply the insecticidalcomposition to the infested article, for example, a low molecularweight, normally gaseous carrying agent. The active insecticidalcomponent, such as propane, butane, the Freons, etc., may be compressedand liquefied into a small bomb containing the insecticide. Upon releaseof pressure from the bomb, the liquefied carrier vaporizes and suspendsa quantity of the active components therein, thus providing a convenientspraying method of applying the insecticide. The active component mayalso be dissolved in a liquid carrier, such as kerosene, an alcohol,ester, ketone, etc., and the resulting solution atomized by a suitablespraying device.

The present invention is further illustrated with respect to specificembodiments thereof in the following examples which, however, are notintended to limit the generally broad scope of the present invention instrict accordance therewith.

Example I A mixture of 102 g. of dicyclopentadiene and 200 g. of2,3-dichloro-1-propene was heated at a temperature in the range of from180 to 200 C. in a glass liner of a rotating autoclave under 30atmospheres of initial nitrogen pressure for a period of about 4.5hours. At the end of this time the liner and contents thereof werecooled to room temperature, the nitrogen vented and the reaction productwas separated from unreacted starting materials. The reaction productwas subjected to fractional distillation at reduced pressure and the cutboiling at 7577 C. (at 4 mm. pressure) or 221-223 C. (at 760 mm.) wasseparated. The cut amounted to 118 g. of 5-chloro-S-chloromethyl-Z-norbornene having a refractive index in therange of from 1.5185 to 1.5205.

The 5-chloro-5-chloromethyl-2-norbornene was partiallydehydrochlorinated by refluxing 43 g. of product prepared as abovedescribed with a solution of 15 g. of potassium hydroxide in n-propylalcohol at 95 C. for 9 hours. Filtration yielded 9.3 g. of potassiumchloride. The filtrate was then distilled, about 120 cc. of overheadboiling at 87-97 C. being obtained, while the temperature of thealcoholic solution rose to 102 C. The solution was refluxed at 102 C.for an additional twelve hours, after which it was cooled and theprecipitated potassium chloride (1.2 g.) was filtered oif. Water (about800 cc.) was added to the filtrate as well as to the above-mentioneddistillate and the product was ex tracted with pentane. The pentaneextract, which was water washed to remove any dissolved alcohol, wasthen dried over potassium carbonate and fractionally distilled frompotassium carbonate. There was obtained 10 g. of liquid boiling from 89C. at 52 mm. to 79 C. at 29 mm., converted boiling point: (172-176 C. at760 mm.); refractive index, r1 1.51 57-1.5166. The infrared spectrum ofthis material indicated that it contained both the cis-ethylenic doublebond such as is found in 2-norbornene and a trisubstituted ethylenicdouble bond exo to the ring. It was apparent that the product consistedchiefly of 5-chloromethylene-2-norbornene mixed with a smaller amount of2-chloromethyl-2,5-norbornadiene.

Example II In this experiment the 5-chloro-S-chloromethyl-Z-norbornenewas prepared in a manner similar to that set forth in Example I above.The 5-chloro-5-chloromethyl-2- norbornene was heated under reflux withan ethyl alcohol solution of potassium hydroxide at 80 C. for a periodof approximately 16 hours, after which time the reaction product wasseparated and subjected to fractional distillation under reducedpressure.

The cut boiling at 6972 (at 19 mm. pressure) or 174175 C. (at 760 mm.)was separated out. This cut, comprising 5-chloromethylene-2-norborneneand 2- chloromethyl-Z,S-norbornadiene, having a refractive index of1.5183 was subjected to analysis. The results of this analysis are setforth below.

Analysis-Calculated for C H Cl: C, 68.33; H, 6.45; C], 25.22. Found: C,67.64; H, 6.65; Cl, 25.66.

Example III A mixture of 102 g. of dicyclopentadiene and 200 g. of1,3-dichloro-l-propene was heated at a temperature in the range of fromabout 180 to about 200 C. in a glass liner of a rotating autoclave under30 atmospheres of initial nitrogen pressure for a period of about 4.5hours. At the end of this time the liner and contents thereof werecooled to room temperature, the nitrogen was vented and the reactionproduct comprising 6-chloro-5-chloromethyl-2-norbornene was separated.

A solution of 40 g. of the 6-chloro-5-chloromethyl-2- norbornene and 15g. of potassium hydroxide in 150 g. of n-propyl alcohol was heated underreflux at -98 C. for 9 hours. The potassium chloride which hadprecipitated (8 g.) was filtered oif and the filtrate was distilled toremove about cc. of overhead at 87-96 C. The temperature of the solutionrose to 100 C. at which temperature it was refluxed for an additional 11hours. The product was permitted to cool and was then filtered yielding4.0 g. additional potassium chloride. The filtrate was combined with theoverhead, about 1 liter of Water was added and the product was extractedwith pentane. The pentane extract was washed with water, dried anddistilled from potassium carbonate. There was obtained 11.5 g. of afraction boiling from 90 C. at 60 mm. to 88 C. at 38 mm., convertedboiling point: (l69l79 C. at 760 mm.); refractive index, 11 15116-15130.Infra-red inspection of the product showed that it consisted chiefly ofa mixture of 6-chloro-5-methylene-2-norbornene and2-chlorornethyl-2,5-n0rbornadiene.

Example IV A mixture of cyclopentadiene and 2,4-dichloro-1-butene isheated at approximately 200 C. in a glass liner of a rotating autoclaveunder 30 atmospheres under initial nitrogen pressure for a period oftime of about 5 hours. At the end of this time, the liner and contentsthereof are cooled to room temperature. The nitrogen gas is vented andthe reaction product is subjected to fractional distillation underreduced pressure. The cut, comprising 5-chloro-S-(Z-chloroethyl)-2-norbornene is separated out.

The above mentioned norbornene is heated under reflux with an ethylalcohol solution of potassium hydroxide at a temperature ofapproximately 80 C. for about 16 hours. At the end of this time thereflux vessel and the contents thereof are cooled to room temperatureand the reaction product subjected to fractional distillation underreduced pressure. The cut, comprising5-(2-chloroethylidene)-2-norbornene and2-(2-chloroethyl)-2,5-norbornadiene is separated and purified byconventional means.

Example V A mixture of cyclopentadiene and 2,3-dibromo-1-propene isheated at a temperature in the range of from about 180 to about 200 C.in a glass liner of a rotating autoclave under 30 atmospheres of initialnitrogen pressure for a period of time of about 5 hours. At the end ofthis time the liner and contents thereof are cooled to room temperature,the nitrogen is vented and the reaction product is subjected tofractional distillation under reduced pressure, the cut comprisingS-bromo-S-bromomethyl-Z-norbOrnene being separated out. Theaforementioned norbornene is heated under reflux with an ethanolsolution of potassium hydroxide at a temperature of approximately 80 C.for a period of about 10 hours. At the end of this time the refluxvessel and contents In this example cyclopentadiene and2,3,3-trichloro-1- propene are condensed in a manner similar to that setforth in the above examples. The reaction product comprisingS-chloro-S-dichloromethyl-Z-norbornene is separated and recovered byconventional means hereinbefore described. The aforementioned norborneneis partially dehalogenated by heating under reflux with a propyl alcoholsolution of potassium hydroxide at a temperaure of about 85 C. for about10 hours. At the end of this time the reaction product is subjected tofractional distillation and the cut, comprising5-dichloromethylene-2-norbornene and 2-dichloromethyl-2,5-norbornadieneis separated and recovered.

I claim as my invention:

1. A process for the preparation of a halosubstituted bicycloalkadienewhich comprises condensing a conjugated cycloalkadiene with ahalo-olefin having the general formula Q Q in which R is a haloalkylradical, Q and Q are radicals selected from the group consisting ofhydrogen and halogen radicals, only one of said Q and Q radicals beinghalogen, and R is a radical selected from the group consisting ofhydrogen, alkyl, halogen, haloalkyl, cycloalkyl and aryl radicals,thereby forming a haloalkylhalobicycloalkene, and partiallydehydrohalogenating said alkene in the persence of a dehydrohalogenatingagent selected from the group consisting of alkali metal hydroxides,alkaline earth metal hydroxides, alkali metal alkoxides and amines at atemperaure in the range of from about 50 to about 250 C. to form ahalo-substituted bicycloalkadiene.

2. A process for the preparation of a halo-substituted bicycloalkadienewhich comprises condensing a conjugated cycloalkadiene with ahalo-olefin having the general formula V in which R is a haloalkylradical, Q and Q are selected from the group consisting of hydrogen andhalogen radicals, only one of said Q and Q radicals being halogen, and Ris a radical selected from the group consisting of hydrogen, alkyl,halogen, haloalkyl, cycloalkyl and aryl radicals, thereby forming ahaloalkylhalobicycloalkene, and partially dehydrohalogenatingsaid'alkene in the presence of a dehydrohalogenating agent comprising analkali metal hydroxide and an organic solvent at a temperature in therange of from about 50 to about 250 C. to form a halo-substitutedbicycloalkadiene.

3. A process for the preparation of a halo-substituted bicycloalkadienewhich comprises condensing a conjugated cycloalkadiene with ahalo-olefin having the general formula in which R is a haloalkylradical, Q and Q are selected from the group consisting of hydrogen andhalogen radicals, only one of said Q and Q radicals being halogen, and Ris a radical selected from the group consisting of hydrogen, alkyl,halogen, haloalkyl, cycloalkyl and aryl radicals, thereby forming ahaloalkylhalobicycloalkene, and partially dehydrohalogenating saidalkene in the presit i 12 ence of a dehydrohalogenating agent'comprisingpotassium hydroxide and alcohol at a temperature inthe range of fromabout 50? to about 250 C. to form ahalo-substituted bicycloalkadiene,

4. A process for the preparation of a halo-substituted bicycloalkadienewhich comprises condensing a conjugated cycloalkadiene with ahalo-olefin having the general formula in which R is a haloalkylradical, Q and Q are selected 0 from the group consisting of hydrogenand halogen radicals, only one of said Q and Q radicals being halogen,and R is a radical selected from the group consisting of hydrogen,alkyl, halogen, haloalkyl, cycloalkyl 'and aryl radicals, therebyforming a haloalkylhalobicycloalkene, and partially dehydrohalogenatingsaid alkene in the presence of a dehydrohalogenating agent comprisingpotas sium hydroxide and ethanol at a temperature in the range of fromabout 50 to about 250 C. to form a halo-substituted bicycloalkadiene. V

5. A process for the preparation of a halo-substituted bicycloalkadienewhich comprises condensing a conjugated cycloalkadiene with ahalo-olefin having the general formula I Y Q Q in which R is a haloalkylradical, Q and Q are selected from the group consisting of hydrogen andhalogen radicals, only one of said Q and Q radicals being halogen, and Ris a radical selected from the group consisting of hydrogen, alkyl,halogen, haloalkyl, cycloalkyl and aryl radicals, thereby forming ahaloalkylhalobicycloalkene, and partially dehydrohalogenating saidalkenein the presence of a dehydrohalogena-ting agent comprisingpotassium hydroxide and a propyl alcohol at a temperature in the rangeof from about 50 to about 250 C. to form a halo-substitutedbicycloalkadiene.

6. A process for the preparation of a halo-substituted bicycloalkadienewhich comprises condensing a conjugated cycloalkadiene with ahalo-olefin having the general formula V in which R is a haloalkylradical, Q andQ' are selected from the group consisting of hydrogen andhalogen radicals, only. one of said Q and Q radicals being halogen, andR is a radical selected from the group consisting-0f hydrogen, alkyl,halogen, haloalkyl, cycloalkyl and aryl radicals, thereby forming ahaloalkylhalobicycloalkene, and partially dehydrohalogenating saidalkene in the presence of a dehydrohalogenating agent comprising sodiumhydroxide and ethanol at a temperature in the range of from. about 50 toabout 250 C. to form a halo-substituted bicycloalkadiene.

' 7; A process for the preparation of ahalo-substitutedbicycloheptadiene which comprises condensing cyclopentadiene with ahalo-olefin having the general formula in which R is a haloalkylradical, Q and Q are radicals selected from the group consisting ofhydrogen and halogen radicals, only one of said Q and Q radicals beinghalogen, and R is a radical selected fromthe group consisting ofhydrogen, alkyl, halogen, haloalkyl, cycloalkyl and aryl radicals,thereby forming a haloalkylhalobicycloheptene, and partiallydehydrohalogenating said heptene in the presence of adehydrohalogenating agent comprising an alkali metal hydroxide and anorganic solvent at a temperature in the range of from about 50 to about250 C. to form a halo-substituted bicycloheptadiene.

8. A process for the preparation of a halo-substituted bicycloheptadienewhich comprises condensing cyclopentadiene with 2,3-dich1oro-1-propene,thereby forming chloro-S-chloromethyl-2-norbornene, and partiallydehydrohalogenating said heptene in the presence of potassium hydroxideand ethanol at a temperature in the range of from about 75 to about 200C. to form S-chloromethylene2-norbornene and2-chloromethy1-2,S-norbornadiene.

9. A process for the preparation of a halo-substituted bicycloheptadienewhich comprises condensing cyclopentadiene with 2,3-dibromo-1-propene,thereby forming 5- bromo-S-bromomethyl-2-norbornene, and partiallydehydrohalogenating said heptene in the presence of potassium hydroxideand ethanol at a temperature in the range of from about 75 to about 200C. to form S-bromomethylene-2-norbornene and 2 bromo-2,5norbornadiene.

10. A process 'for the preparation of a halo-substitutedbicycloheptadiene which comprises condensing cyclopentadiene with1,3-dichloro-1-propene, thereby forming 5- chloro-G-chloromethyl--norbornene, and partially dehydrohalogenating said norbornene withpotassium hydroxide and ethanol at a temperature in the range of fromabout 75 to about 200 C. to form 6-chloro-5-methylene- 2-norbornene and2'ch1oromethy1-2,S-norbornadiene.

111. A process for the preparation of a halo-substitutedbicycloheptadiene which comprises condensing 2,3,3-trichloro-l-propenewith cyclopentadiene, thereby forming5-chloro-5-dichloromethyl-2anorbornene, and partiallydehydrohalogenating said norbornene with potassium hydroxide andpropanol at a temperature in the range of from about to about 200 C. toform S-dichloromethylene 2 norbornene and2-dich1oromethyl-2,5-norbornadiene.

12. A process for the preparation of a halo-substitutedbicycloheptadiene which comprises condensing 2,4-dichloro-lbutene withcyclopentadiene, thereby forming5-chloro-5-(2-chloroethyl)-2-norbornene, and partiallydehydrohalogenating said norbornene in the presence of potassiumhydroxide and ethanol at a temperature in the range of from about 75 toabout 200 C. to form 5-(2- chloroethylidene-Z-norbornene and2-(2-ch1oroethyl)-2,5- norbornadiene.

13. A S-haloalkylidene-Z-norbornene.

14. 5-chloromethylene-2-norbornene.

15. S-bromomethyleneQ-norbornene.

16. 6-chloro-5methylene-Z-norbornene.

17. 5-diohloromethylene-2-norbornene.

18. 5-(2-chloroethylidene)-2-norbornene.

References Cited in the file of this patent UNITED STATES PATENTS2,351,311 Alder et a1 June 13, 1944 2,717,851 Lidov Sept. 13, 19552,960,541 Elam et a1 Nov. 15, 1960

1. A PROCESS FOR THE PREPARATION OF A HALOSUBSTITUTED BICYCLOALKADIENEWHICH COMPRISES CONDENSING A CONJUGATED CYCLOALKADIENE WITH AHALO-OLEFIN HAVING THE GENERAL FORMULA
 13. A5-HALOALKYLIDENE-2-NORBORNENE.